JP2817346B2 - Method for producing conductive polymer using fluorine gas - Google Patents
Method for producing conductive polymer using fluorine gasInfo
- Publication number
- JP2817346B2 JP2817346B2 JP2106839A JP10683990A JP2817346B2 JP 2817346 B2 JP2817346 B2 JP 2817346B2 JP 2106839 A JP2106839 A JP 2106839A JP 10683990 A JP10683990 A JP 10683990A JP 2817346 B2 JP2817346 B2 JP 2817346B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- fluorine gas
- conductivity
- present
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、フッ素ガスと重合性単量体との反応による
導電性重合体の簡便な製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a simple method for producing a conductive polymer by reacting a fluorine gas with a polymerizable monomer.
（従来技術とその問題点） 導電性高分子として例えば、ポリアセチレン、ポリピ
ロール、ポリパラフェニレンなどのπ共役系ポリマーが
あり、これらをAsF5、I2などによりドープすることによ
り導電性を示すようになる。この有機高分子の導電性を
利用してポリマーバッテリー、エレクトロクロミック材
料（表示装置）、太陽電池、トランジスタ・ダイオー
ド、センサなど巾広い用途が考えられる。(Prior art and its problems) Examples of conductive polymers include π-conjugated polymers such as polyacetylene, polypyrrole, and polyparaphenylene. Doping these with AsF 5 , I 2, or the like will provide conductivity. Become. A wide range of applications such as polymer batteries, electrochromic materials (display devices), solar cells, transistors and diodes, and sensors can be considered by utilizing the conductivity of the organic polymer.
しかしながら、現在開発中の導電性高分子材料は、耐
環境性に劣るもの、脆性が大きく加工性が乏しいもの等
が多いのが現状である。However, at present, there are many conductive polymer materials currently under development that have poor environmental resistance, are brittle, and have poor workability.
導電性重合体の製造方法としては、白金などの電極表
面に重合膜を形成させる電解重合法が一般的に行われて
いる。重合中にドーピングも可能になっている。この他
にも、塩化第二鉄を樹脂などの基板に分散させ、ピロー
ルなどの重合性単量体の蒸気と接触させる方法がある
が、操作に手間がかかるとともに反応時間もかかる、と
いう問題がある。As a method for producing a conductive polymer, an electrolytic polymerization method for forming a polymer film on the surface of an electrode such as platinum is generally performed. Doping during the polymerization is also possible. In addition, there is a method of dispersing ferric chloride on a substrate such as a resin and bringing it into contact with the vapor of a polymerizable monomer such as pyrrole.However, the operation is troublesome and the reaction time is long. is there.
（発明の目的） 本発明は、上記の事情に鑑み、より簡便な装置、手法
で、短時間にフィルム状、あるいは、粉末状の導電性重
合体を容易に製造し得る、導電性重合体の製造方法を提
供することを目的とする。(Object of the Invention) In view of the above circumstances, the present invention relates to a conductive polymer which can easily produce a film-like or powdery conductive polymer in a short time with a simpler apparatus and method. It is intended to provide a manufacturing method.
本発明者らは、上記の目的を達成すべく、研究を重ね
た結果、低温で重合性単量体とフッ素ガスとを直接反応
させることにより、目的を達成し得ることを見出し、本
発明に到達した。The present inventors have conducted various studies to achieve the above object, and as a result, have found that the object can be achieved by directly reacting a polymerizable monomer with fluorine gas at a low temperature. Reached.
（発明の構成） 本発明は、フッ素ガスと重合性単量体とを反応させる
ことからなる導電性重合体の製造法を提供する。(Constitution of the Invention) The present invention provides a method for producing a conductive polymer, which comprises reacting a fluorine gas with a polymerizable monomer.
本発明はまた、前記製造方法であって、単量体がピロ
ール、チオフェン、フランからなる群から選ばれるもの
である方法を提供する。The present invention also provides the method as described above, wherein the monomer is selected from the group consisting of pyrrole, thiophene, and furan.
本発明はまた、前記の製造方法であって、重合を０〜
−80℃の温度で実施する方法を提供する。The present invention also relates to the above production method, wherein
A method is provided which is carried out at a temperature of -80 ° C.
本発明はまた、前記の製造方法であって、チッ素ガス
で５〜20容量％に希釈したフッ素ガスを用いる方法を提
供する。The present invention also provides a method as described above, wherein a fluorine gas diluted to 5 to 20% by volume with nitrogen gas is used.
本発明に用いられる重合性単量体は、ピロール、チオ
フェン、フラン等が挙げられる。通常は、ピロールが最
も好ましく用いらる。Examples of the polymerizable monomer used in the present invention include pyrrole, thiophene, and furan. Usually, pyrrole is most preferably used.
すなわち、本発明によれば、ピロールをアセトニトリ
ル、ジクロロメタン、四塩化炭素などの有機溶媒に溶か
し、−80〜０℃の温度範囲で、チッ素ガスなどの不活性
ガスで希釈した５〜20容量％のフッ素ガスと短時間反応
させることにより、容易に導電性重合体を生成させるこ
とを特徴とする導電性重合体の製造方法が得られる。本
発明方法におけるチッ素等の不活性ガス雰囲気下におけ
るフッ素ガス濃度は、５〜20容量％の範囲である。より
好ましくは10容量％前後である。フッ素ガス濃度が５容
量％未満では、反応終了に時間がかかり導電率が低い。
20容量％を越えると、反応が激しくなり、重合の他にも
分解を起るため、導電率も低くなる。例えば、フッ素10
容量％−チッ素90容量％で、ピロールと２時間反応させ
た場合には、ポリピロールの導電率が10-10S・cm-1のオ
ーダーであるのに対し、10-2S・cm-1のオーダーの導電
性重合体が得られる。また、反応温度は、フッ素ガスの
反応性を抑制する意味からも−80〜０℃の範囲が望まし
い。より好ましくは、−80〜−40℃の範囲である。−80
℃よりも反応温度が低いと重合体の生成に時間がかか
り、０℃を越えると、反応が激しくなり、導電率も低く
なる。That is, according to the present invention, pyrrole is dissolved in an organic solvent such as acetonitrile, dichloromethane, and carbon tetrachloride, and diluted with an inert gas such as nitrogen gas in a temperature range of −80 to 0 ° C. to 5 to 20% by volume. A method for producing a conductive polymer, characterized in that a conductive polymer is easily formed by reacting with a fluorine gas for a short time. The fluorine gas concentration in an inert gas atmosphere such as nitrogen in the method of the present invention is in the range of 5 to 20% by volume. More preferably, it is around 10% by volume. When the fluorine gas concentration is less than 5% by volume, it takes a long time to complete the reaction, and the conductivity is low.
If the content exceeds 20% by volume, the reaction becomes violent and decomposition occurs in addition to polymerization, so that the electric conductivity is lowered. For example, fluorine 10
When reacting with pyrrole at 2% by volume at 90% by volume of nitrogen, the conductivity of polypyrrole is on the order of 10 −10 S · cm −1 , whereas the conductivity of polypyrrole is 10 −2 S · cm −1. Is obtained. Further, the reaction temperature is preferably in the range of -80 to 0C from the viewpoint of suppressing the reactivity of the fluorine gas. More preferably, it is in the range of -80 to -40C. −80
If the reaction temperature is lower than 0 ° C., it takes a long time to form a polymer.
上記の重合反応の経過から、本発明の導電性重合体の
製造方法において、フッ素ガスは重合開始剤として作用
すると同時に、ドーパントとして重合体分子中にとりこ
まれるものと推測される。なお、本発明において、導電
性重合体とは、導電率が10-3S・cm-1以上のオーダーで
あることを意味する。From the progress of the above polymerization reaction, it is presumed that in the method for producing a conductive polymer of the present invention, fluorine gas acts as a polymerization initiator and is incorporated into a polymer molecule as a dopant. In the present invention, the conductive polymer means that the conductivity is on the order of 10 −3 S · cm −1 or more.
本発明によれば、ガラス板などの基板を反応溶液中に
浸漬し、フッ素ガスと反応させることにより、ガラス板
などの基板上に重合膜が生成する。According to the present invention, a polymer film is formed on a substrate such as a glass plate by immersing the substrate such as a glass plate in a reaction solution and reacting with a fluorine gas.
また、ガラス板などの基板にピロールを塗布し、これ
とフッ素ガスとを短時間接触させることにより、容易に
均一な導電性重合膜を形成することもできる。In addition, a uniform conductive polymer film can be easily formed by applying pyrrole to a substrate such as a glass plate and bringing it into contact with fluorine gas for a short time.
したがって、本発明方法により、従来法に比べて簡便
に導電性重合体を製造できる。さらに、本発明によれ
ば、同時に導電性重合膜と導電性重合粉体を得ることも
できる。Therefore, according to the method of the present invention, a conductive polymer can be produced more easily than in the conventional method. Further, according to the present invention, a conductive polymer film and a conductive polymer powder can be obtained at the same time.
（発明の具体的開示） 次に、本発明を実施例により具体得に説明するが、こ
れらの実施例は、本発明の範囲を規定するものではな
い。(Specific Disclosure of the Invention) Next, the present invention will be described more specifically with reference to examples, but these examples do not limit the scope of the present invention.
また、実施例においては、容量％を％で示す。導電率
の測定は、四端子法によりおこなった。Further, in Examples,% by volume is indicated by%. The conductivity was measured by a four-terminal method.
実施例１ 撹はん子の入った100mlの３口フラスコに、ピロール
1.50g（0.022モル）、ジクロロメタン50.04g（0.59モ
ル）を入れ、−78℃まで冷却する。フッ素10％−チッ素
90％の混合ガスを140cc/分の流速で２時間導入した。反
応終了後、チッ素ガスをバブリングさせ、反応溶液中の
フッ素ガスを除去した。フラスコ壁に生成したポリピロ
ール膜を剥して導電率を測定したところ、8.1×10-2S・
cm-1であった。また、同時に生成したポリピロール粉末
を圧粉体にして、その導電率を測定したところ、5.7×1
0-3S・cm-1であった。Example 1 Pyrrole was placed in a 100 ml three-necked flask containing a stirrer.
1.50 g (0.022 mol) and 50.04 g (0.59 mol) of dichloromethane are added and cooled to -78 ° C. Fluorine 10%-nitrogen
A 90% mixed gas was introduced at a flow rate of 140 cc / min for 2 hours. After the completion of the reaction, nitrogen gas was bubbled to remove fluorine gas in the reaction solution. When the conductivity was measured by peeling off the polypyrrole film formed on the flask wall, 8.1 × 10 -2 S
cm -1 . The polypyrrole powder produced at the same time was made into a green compact, and its conductivity was measured.
It was 0 -3 S · cm -1 .
実施例２ 実施例１と同様の実験装置を用い、アセトニトリル
（1.22モル）中で反応温度−40℃にしてピロール（0.03
0モル）とフッ素ガスとの反応を行った。得られたポリ
ピロール膜の導電率を測定したところ、1.4×10-2S・cm
-1であった。Example 2 Using the same experimental apparatus as in Example 1, pyrrole (0.03 mol) was prepared in acetonitrile (1.22 mol) at a reaction temperature of -40 ° C.
0 mol) and fluorine gas. When measuring the conductivity of the obtained polypyrrole film, 1.4 × 10 -2 Scm
It was -1 .
実施例３ 実施例１と同様の実験装置を用い、ガラス板を反応溶
液中（溶媒：アセトニトリル）に浸しておき、−40℃で
１時間反応を行った。ガラス板上に生成したポリピロー
ル膜の導電率を測定したところ、1.2×10-2S・cm-1であ
った。Example 3 Using the same experimental apparatus as in Example 1, a glass plate was immersed in a reaction solution (solvent: acetonitrile), and a reaction was performed at −40 ° C. for 1 hour. The measured conductivity of the polypyrrole film formed on the glass plate was 1.2 × 10 −2 S · cm −1 .
実施例４ ガラス板にピロールを塗布しておき、これをあらかじ
め−40℃に冷却したガラス製反応容器に入れ、フッ素10
％−チッ素90％の混合ガスを５分間接触させたところ、
導電率2.5×10-3S・cm-1のポリピロール膜が得られた。Example 4 A glass plate was coated with pyrrole, placed in a glass reaction vessel previously cooled to −40 ° C.,
When a mixed gas of 90% and 90% nitrogen was contacted for 5 minutes,
A polypyrrole film having a conductivity of 2.5 × 10 −3 S · cm −1 was obtained.
比較例１ 実施例１と同様な方法で、アセトニトリル中、−40℃
で、フッ素30％−チッ素70％の混合ガスでピロールと反
応を行ったところ、激しい反応となり、得られたポリピ
ロール膜の導電率も6.5×10-5S・cm-1と低くなった。Comparative Example 1 In the same manner as in Example 1, -40 ° C. in acetonitrile
When a reaction was performed with pyrrole using a mixed gas of 30% fluorine and 70% nitrogen, a vigorous reaction was caused, and the conductivity of the obtained polypyrrole film was lowered to 6.5 × 10 −5 S · cm −1 .
比較例２ 実施例１と同様な方法で、アセトニトリル中、−40℃
で、フッ素１％−チッ素99％の混合ガスでピロールと４
時間反応を行ったところ、導電率8.4×10-4S・cm-1のポ
リピロール膜が得られた。Comparative Example 2 In the same manner as in Example 1, -40 ° C. in acetonitrile
In a mixed gas of 1% fluorine-99% nitrogen, pyrrole and 4%
After performing the reaction for a time, a polypyrrole film having a conductivity of 8.4 × 10 −4 S · cm −1 was obtained.
比較例３ 実施例１と同様な方法で、アセトニトリル中、室温
で、ピロールと反応を行なったところ、かなり激しい反
応となり、導電率1.2×10-6S・cm-1の不均一なポリピロ
ール膜が得られた。Comparative Example 3 When a reaction was performed with pyrrole in acetonitrile at room temperature in the same manner as in Example 1, the reaction became quite violent, and a nonuniform polypyrrole film having a conductivity of 1.2 × 10 −6 S · cm −1 was obtained. Obtained.
（発明の効果） 以上のように本発明の方法を実施することにより、簡
便な方法で導電性重合膜および導電性重合粉体を製造す
ることが可能であり、基板の形状を変えることにより様
々な形状に導電性膜を加工できるので工業的に極めて価
値がある。(Effect of the Invention) By carrying out the method of the present invention as described above, a conductive polymer film and a conductive polymer powder can be produced by a simple method, and various methods can be performed by changing the shape of the substrate. Since the conductive film can be processed into various shapes, it is extremely valuable industrially.
Claims (4)
れた重合性単量体に反応させることを特徴とする、導電
性重合体の製造方法。1. A method for producing a conductive polymer, comprising reacting fluorine gas with a polymerizable monomer selected from aromatic heterocyclic compounds.
らなる群から選ばれるものである請求項１に記載の導電
性重合体の製造方法。2. The method for producing a conductive polymer according to claim 1, wherein the monomer is selected from the group consisting of pyrrole, thiophene, and furan.
１または２に記載の導電性重合体の製造方法。3. The method for producing a conductive polymer according to claim 1, wherein the polymerization is carried out at a temperature of 0 to -80 ° C.
素ガスを用いる請求項１ないし３のいずれか１項に記載
の導電性重合体の製造方法。4. The method for producing a conductive polymer according to claim 1, wherein a fluorine gas diluted to 5 to 20% by volume with an inert gas is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2106839A JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2106839A JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH044221A JPH044221A (en) | 1992-01-08 |
| JP2817346B2 true JP2817346B2 (en) | 1998-10-30 |
Family
ID=14443867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2106839A Expired - Lifetime JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2817346B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003607A1 (en) * | 1985-12-06 | 1987-06-18 | Showa Denko Kaubshiki Kaisha | Polymers having isoindole structure and process for their preparation |
-
1990
- 1990-04-23 JP JP2106839A patent/JP2817346B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH044221A (en) | 1992-01-08 |
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